CN107112302A - Property reinforcer for clear coat and nesa coating - Google Patents

Abstract

The present invention relates to optical clear film, it may include the coating of Nano diamond to introduce desired properties, such as hardness, good thermal conductivity and the dielectric constant through raising.In general, nesa coating may be formed to have the desired property enhancing nano-particle being contained in transparency conducting layer and/or coating.Property enhancing nano-particle can be formed by the material with big hardness parameter, big thermal conductivity and/or big dielectric constant.Suitable polymer is incorporated to as adhesive in the layer for strengthening nano-particle with the property.Can solution applying implenent have property strengthen nano-particle the coating and description corresponding solution.

Description

Property reinforcer for clear coat and nesa coating

To the cross reference of related application

Present application requires that the entitled of Weir card (Virkar) et al. filed in 19 days December in 2014 " is used for clear coat And property reinforcer (the Property Enhancing Fillers for Transparent of nesa coating Coatings and Transparent Conductive Films) " U.S. Patent Application No. 14/577,669 and " the property enhancing for being used for coating and nesa coating is filled out for Weir card (Virkar) et al. filed in 3 days October in 2014 entitled Expect (Property Enhancing Fillers for Coatings and Transparent Conductive Films) " U.S. Provisional Application case the 62/059th, 376 priority, two case is incorporated herein by reference.

Technical field

The present invention relates to be mounted with property enhancing nano-particle (for example, contribute to hardness and wearability, thermal conductivity and/or The nano-particle of high-k) thin polymer film.The invention further relates to incorporate to be mounted with property enhancing nanoparticle The thin polymeric layers (its can or can not be in the layer and/or the coating associated with transparency conducting layer of electrical conductivity are provided) of son Nesa coating.The invention further relates to the transparent film based on polymer including Nano diamond.Moreover, it relates to wrap The property enhancing nano-particle that include the polymer through dissolving, is dispersed through, other optional compositions are (for example, processing aid or stably Composition) and optional metal nanometer line coating solution.

Background technology

Transparent polymer film is used in broad range of product.Although the film can be used for many purposes, the film leads to Certain protection to various machineries and/or environmental assaults is often provided.The protection provided by film can be for the structure and described of underliing Film itself both, this is due to (for example) that film has the scraped surface can be by reducing transparency and increase is fuzzy or turbidity drop Level film wants performance.The protection on surface during the use of final products and formed product processing and for being assembled to All can be important during the conveying of component in the product.

Functionality film can provide important effect in a series of environment.For example, when electrostatic can be unwanted or When dangerous, conducting film can be important for static dissipation.Optical film can be used for providing various functions, such as polarisation, anti-reflective Penetrate, phase shift, blast or other functions.High quality displayer may include one or more optical coatings.

Transparent conductor can be used for some photovoltaic applications, comprising such as touch-screen, liquid crystal display (LCD), flat-panel monitor, Organic Light Emitting Diode (OLED), solar cell and smart window.In history, tin indium oxide (ITO) is attributed to it highly conductive The relative high grade of transparency under rate turns into preferred material.However, there are some shortcomings in ITO.For example, ITO is to need to use The brittle ceramic of sputtering (its be related to high temperature and vacuum and therefore can relatively slow manufacturing process) deposition.Additionally, it is known that ITO Easily ftracture on flexible substrates.

The content of the invention

In the first aspect, the present invention relates to optical texture, the optical texture includes transparent substrates and including polymer The coating of adhesive and Nano diamond.

In another aspect, the present invention relates to nesa coating, the nesa coating includes transparent substrates, electrically conducting transparent Layer and the protective coating including polymer adhesive and nano-particle.In certain embodiments, the nano-particle has and not surpassed Cross about 100nm average primary particle diameter and formed by following material：Block Vickers hardness with least about 1650HV Material；High thermal conductivity material, it is selected from the group being made up of the following：Diamond, graphene, silicon nitride, boron nitride, nitridation Aluminium, GaAs, indium phosphide or its mixture；And/or high dielectric constant material, it is selected from the group being made up of the following：Titanium Sour barium, strontium titanates, lead titanates, lead zirconium titanate, CaCu 3 Ti 4 O and its mixture.

In additional aspect, the present invention relates to nesa coating, the nesa coating includes transparent substrates and including poly- The transparency conducting layer of compound adhesive, sparse metallic conductive element and nano-particle.In certain embodiments, the nano-particle There can be no more than about 100nm average primary particle diameter and can be formed by following material：Block dimension with least about 1650HV The material of family name's hardness；High thermal conductivity material, it is selected from the group being made up of the following：Diamond, graphene, silicon nitride, nitrogen Change boron, aluminium nitride, GaAs, indium phosphide or its mixture；And/or high dielectric constant material, it is selected from and is made up of the following Group：Barium titanate, strontium titanates, lead titanates, lead zirconium titanate, CaCu 3 Ti 4 O and its mixture.

In other side, the present invention relates to the optical texture for including transparent substrates and clear coat.The clear coat It may include polymer adhesive and the average once grain with no more than about 100nm from about 0.05 weight % to about 30 weight % The nano-particle of sub- diameter, and can have the pencil hardness bigger at least about 1 grade than the pencil hardness of the clear coat without filler And the total transmission reduction of no more than about 5% visible ray for being attributed to transparent hard-coating layer.

In addition, the present invention relates to the solution for including solvent, curable polymer adhesive and nano-particle.The nanoparticle Son can have no more than about 100nm average primary particle diameter and may include following material：With at least about 1650HV block The material of body Vickers hardness；High thermal conductivity material, it has at least about 30W/ (mK) block thermal conductivity；High-k material Material, it is selected from the group being made up of the following：Barium titanate, strontium titanates, lead titanates, lead zirconium titanate, CaCu 3 Ti 4 O and its mixing Thing, or its mixture.

Brief description of the drawings

Fig. 1 is the various additional transparents layer with sparse metal conducting layer and on the either side of sparse metal conducting layer The fragmentary side view of film.

Fig. 2 is the representative signal patterned structure with three conductive paths formed with sparse metal conducting layer Top view.

Fig. 3 is the schematic diagram of touch sensor of the displaying based on electric capacity.

Fig. 4 is the schematic diagram of touch sensor of the displaying based on resistance.

Fig. 5 is the nesa coating with external coating (it has 10wt% Nano diamonds) under the first magnifying power Scanning electron microscopy (SEM).

Fig. 6 is the SEM image of the nesa coating of Fig. 5 under higher magnifying power.

Fig. 7 is the SEM image of the nesa coating with external coating (it has 5wt% Nano diamonds).

Fig. 8 is the SEM image of the nesa coating with external coating (it has 3wt% Nano diamonds).

Embodiment

The clear coat with polymer substrate is developed, there is the polymer substrate property to strengthen nanoparticulate fillers To provide desired properties in the shallow layer with good optical transparency for coating, such as hardness through raising and/or higher Thermal conductivity.Suitable filler for polymer substrate is including (for example) Nano diamond, and it can be by wanted hardness, through raising Dielectric constant and thermal conductivity are provided to the coating formed with Nano diamond without making optical clarity reduction not equivalent.It is other suitable When nano-particle or its combination can be similarly incorporated in polymer substrate.Nano-particle as filler can be by with high block The material of body hardness number and/or high block thermal conductivity and/or high block dielectric constant is formed.In certain embodiments, by loading The coating of the polymer formation of particle can have no more than about 5 microns of thickness.Enhanced coating can be via Solution coating processes (wherein matrix polymer is dissolved in solvent and nano-particle is scattered in solution) is formed.It is saturating that the coating is applicable to protection Bright conductive layer, but other clear coat applications can effectively utilize enhanced coating described herein.Specifically, it is transparent to lead Electric layer can be formed by metal nanometer line.In extra or alternate embodiment, filler to be directly appended to be used to form sparse The conductive ink of metallic conductive element, wherein having the increase of corresponding hardness and other property after polymer topcoat is coated with Matter is improved.Protective coating can be used for reducing because scraping, the infringement of environmental assaults (for example, diluted acid and diluted alkaline)；Reduce pyrolytic damage；Drop It is low because of high-tension vulnerability and/or to provide other valuable protections.

As described in this article, enhanced loading coating can be formed, the wherein total transmission of visible ray moderately declines.Can be tool The coating for having relatively good mechanical strength introduces various polymer substrates to provide the good high grade of transparency for further enhancing Basis.Generally, the coating with small thickness can be formed, even and if enhanced engineering properties effectively mechanically stable can have The coating of small thickness.In certain embodiments, due to electrical conductivity can be maintained via thin external coating, therefore for using adjacent Small thickness may be needed for bright conductive layer.Therefore, with no more than about 25 microns and micro- no more than 1 in certain embodiments In the case of the average thickness of rice, and the coating of typically at least about 50nm thickness, notable mechanical stability can be obtained.Furthermore, it is possible to The thermal conductivity properties of enhanced coating are needed with heat dissipation, to reduce heating infringement.Improved thermal conductivity can provide it Its desirable purposes is for application-specific.Coating with high dielectric filler can be used for prevent sparse metal conducting layer by To high voltage infringement.

Good coat property is usually directed to the fine dispersion liquid to form nanoparticulate fillers in the solution of matrix polymer, To cause gained coating that there is reduced particles aggregate effect.Nanoparticulate fillers generally being averaged with no more than about 100nm Primary particle diameter, to cause particle to be incorporated into the shallow layer of relative smooth and so that particle and change optics within bounds Property.In general, coating has no more than about 70 weight % nanoparticle-loaded.In coating solution polymer adhesive and The concentration of filler grain, which may be adjusted to produce solution, wants coating performance, the thickness of such as viscosity and final coating.Coating Once the ratio of the concentration of solid may be adjusted to coating drying and just produce desired coating concentration in solution.The polymer of coating Other means that component can generally radiate or be suitable for polymer adhesive by UV are crosslinked further to strengthen the coating.

In general, property enhancing nanoparticulate fillers can be incorporated into passive state protective coating and/or be introduced directly into In bright conductive layer.Passive state transparent protective coating may or may not be used to cover transparency conducting layer.The common attribute of these coatings is painting The compatibility of cloth solution and the component in gained composite.Compatibility refers to be effectively dispersed in relatively uniform material And the ability of the unacceptable levels of aggregation (for example, by aggegation) without component.Specifically, compatibility can allow material to exist The well distributed formation for thinking the reasonable homogeneous composite to form coating in coating solution is prepared.More homogeneous answers Condensation material is believed to be helpful in the optical property of wanting of coating, such as good transparency and low turbidity.

For passive state coating, coating solution may include solvent, the matrix polymer through dissolving, with selected property The nano-particle of matter, its possible combination and optional additional component.A series of matrix polymers suitable for hyaline membrane can be used, As described below.Wetting agent (for example, interfacial agent) and other processing aids can be used.In general, solvent can be wrapped Include water, organic solvent or its suitable mixture.For active coating, coating solution generally further comprises helping to live The component (for example, metal nanometer line for contributing to electrical conductivity) of property functionality.Two types described in example below The example of coating.For the external coating as the transparency conducting layer based on metal nanometer line, it has been found that be incorporated into the external coating In stabilizer can stable transparent conductive layer electrical conductivity.The stabilizer and the good transparency and technique for maintaining coating solution Compatibility is consistent, and is discussed further below.

On wanted filler, it is attributed to and is wanted with introducing of maintaining that good optical transparency and relative low turbidity be consistent Property, Nano diamond is especially concerned.Diamond is and having that the formation of other forms of graphitic carbon, amorphous carbon and carbon is compareed sp³The crystal habit of the carbon of hybridized orbit.Business Nano diamond could generally have the core of crystalline diamonds carbon, with amorphous The shell of shape and/or graphitic carbon, and be dielectric.The surface chemical property of Nano diamond can reflect synthetic method and possible Additional processing.Functionalized or not functionalized business Nano diamond it can be bought after purification from various suppliers, Set forth below.Nano diamond and macroscopical diamond share high hardness and heat conductivity value, and can be used for will for these properties Desired properties are supplied to the clear coat for incorporating Nano diamond.

The commercially available average primary particle that there is usually no more than about 50nm and 10nm is no more than about in certain embodiments The Nano diamond of diameter, but the nanogold of the average primary particle diameter with no more than about 100nm in certain embodiments Hard rock can be useful.As used herein, unless otherwise instructed, otherwise particle diameter is being averaged along the main shaft of particle Value, it can roughly estimate from Transmission Electron micrograph.Business Nano diamond is synthetically produced with possible surface Modification, and spectral technique can be used to confirm for its overall structure.The surfaction of Nano diamond can adding for Nano diamond Work and useful with the compatibility of specific solvent and adhesive.As described in following instance, business Nano diamond can be well It is scattered in a series of solvents to produce the high quality optical coatings with good transparency and low turbidity.Other nano-particles are filled out Material can have with Nano diamond identical in the range of mean particle diameter.Nano-particle can have approximately spherical shape or Other convenient shapes.One of ordinary skill in the art it will be recognized that cover Nano diamond or other properties enhancing receive Additional range in the range of the clear and definite mean particle diameter above of rice corpuscles, and the scope is within the scope of the present invention.

Nano diamond can provide the hardness of wanted degree and thermal conductivity to the composite coating for incorporating Nano diamond. In addition, diamond is good dielectric so that nanocrystalline diamond composite coating can promote the highfield of film that can be in structural damage Dissipation.Other nano-particles can be similarly incorporated to provide saturating with the good optical of gained coating to incorporating by similarity The compound for the functionality nano-particle that lightness is consistent.In order to form nesa coating, for providing the other suitable of hardness Nano-particle is including (but not limited to) (such as) boron nitride, B₄C, cube BC₂N, carborundum, crystallization alpha-aluminium oxide (sapphire) or its Analog.Contribute to the nano-particle of hardness can be by with least about 1650kgf/mm²The block of the Vickers hardness of (16.18GPa) Body material is formed.

On thermal conductivity, in addition to Nano diamond, graphene, silicon nitride, boron nitride, aluminium nitride, GaAs, indium phosphide And its mixture is equally applicable to introduce high heat conductance.In certain embodiments, high thermal conductivity material can have at least about 30W/ (mK) thermal conductivity, and graphene and diamond have the thermal conductivity among known highest thermal conductivity.Specifically, may be used The high dielectric constant material introduced as nano-particle is including (but not limited to) (such as) barium titanate, strontium titanates, lead titanates, metatitanic acid Lead zirconium, CaCu 3 Ti 4 O and its mixture., can be hard by the pencil to film on the hardness of the coating based on polymer of protectiveness Degree is tested to measure hardness, as described further below.Scratch Resistance is also assessed by using steel wool in the following example.

Coating is generally formed by solution coating.Nano-particle (for example, Nano diamond) can be dispersed through, and then nanometer The dispersion liquid of particle can be blended with the coating solution of polymer adhesive, but process sequence may depend on selection and the particle of solvent Disperse properties and adjust.Nano-particle in coating solution can have from about 0.005wt% to about 5.0wt%, in addition Embodiment in be from about 0.0075wt% to about 1.5wt% and in Additional examples of composition be from about 0.01wt% to about Concentration in the range of 1.0wt%.One of ordinary skill in the art belong in above-mentioned clear and definite scope it will be recognized that covering Excess concentrations scope, and the scope is within the scope of the present invention.

Especially concerned transparent conductive element (for example, film) includes sparse metal conducting layer herein.Conductive layer is usual To be sparse to provide the optical clarity of the desired amount, thus conducting element layer upper metal covering have it is extremely obvious between Gap.For example, nesa coating may include the metal nanometer line deposited along layer, and diafiltration is can provide at the layer Contact to provide suitable conductive path enough.In other embodiments, nesa coating may include molten metal nanostructured Network, it has been observed that electrical property and optical property are wanted in presentation.Unless special instructions, otherwise conduction cited herein in addition Rate refers to electrical conductivity.

Loaded polymer film described herein, which can be provided, is generally used for transparent optical film and saturating particularly for protection The desired properties of sparse metallic conductive element in bright conducting film.The thickness of film can be chosen to be sufficiently thin so that can be sent out via film Raw good electrical conductance.The hardness of film may be such that structure scratch resistance scrape along is deformed, and high heat conductance can promote going divided by limiting for heat It is attributed to heat and the possibility to sparse metallic conductive element is damaged.Independent of specific structure, sparse metallic conductive element easily by Environmental assaults.

In general, various sparse metal conducting layers can be formed by metal nanometer line.It is incorporated herein by reference The entitled of Edward Alden (Alden) et al. " include transparent conductor (the Transparent Conductors of metal nanometer line Comprising Metal Nanowires) " United States Patent (USP) 8,049,333 in describe through handling with flat in junction point Change nano wire to improve the film formed with metal nanometer line of conductance.The Si Ruini gas being incorporated herein by reference Et al. (Srinivas) entitled " patterned transparent conductor and relative manufacturing process (Patterned Transparent Conductors and Related Manufacturing Methods) " United States Patent (USP) 8,748,749 in describe including Surface embedded metal nano wire is to improve the structure of metallic conductivity.It has been found, however, that molten metal nanostructured network exists High conductivity and on transparency and low turbidity want optical property in terms of desired properties.Can commercially appropriate processing Under the conditions of based on chemical technology perform adjacent metal nano wire melting.

Metal nanometer line can be formed by a series of metals, and metal nanometer line is commercially available.Although metal nanometer line is led in itself Electricity, but believe that most resistance in the film based on metal nanometer line are attributed to the abutment between nano wire.Depend on Processing conditions and nano wire property, the sheet resistance for the relative transparent nano wire film being deposited into can be great, such as tens of In hundred million ohm/sq scopes or even more high.Have been proposed in and do not destroy resistance that nano wire film is reduced in the case of optical clarity Various methods.Cryochemistry melting is had found to form metal Nano structure network in reduction resistance while maintaining optical clarity Aspect is extremely effective.

Specifically, the impressive progress on realizing the conducting film based on metal nanometer line is that discovery forms molten metal net The technique easy to control of network, in the molten metal network, the adjacent sections fusion of metal nanometer line.Use various molten sources The melting of metal nanometer line is further described in the U.S. patent application case of following discloses：Entitled " the metal of Weir card et al. Nanometer line network and transparent conductive material (Metal Nanowire Networks and Transparent Conductive Material) " 2013/0341074；Entitled " metal Nano structure network and the transparent conductive material of Weir card et al. The 2013/ of (Metal Nanostructured Networks and Transparent Conductive Material) " 0342221 (application case of ' 221)；" molten metal nanostructured network, the melting with reducing agent are molten for Weir card et al. entitled Liquid and method (Fused MetalNanostructured Networks, Fusing for forming metalolic network Solutions With Reducing Agents and Methods for Forming Metal Networks) " 2014/0238833 (application case of ' 833) and poplar (Yang) et al. it is entitled " saturating based on metal nanometer line and polymer adhesive Bright conductive coating, the processing of its solution and patterning method (Transparent Conductive Coatings Based on Metal Nanowires and Polymer Binders,Solution Processing Thereof,and Patterning Approaches) " 2015/0144380 (application case of ' 380) and the topic with Lee (Li) in application et al. " to be used for metal nanometer line ink (the Metal Nanowire Inks for for forming the nesa coating with melting network The Formation of Transparent Conductive Films With Fused Networks) " United States Patent (USP) Application case 14/448,504, all application cases are incorporated herein by reference.

Nesa coating, which is generally included, contributes to the machinability and/or engineering properties of structure without adversely changing Some components or layer of optical property.Sparse metal conducting layer can be designed to have when being incorporated into nesa coating and want Optical property.Sparse metal conducting layer may or may not further comprise polymer adhesive.Unless otherwise instructed, otherwise to thickness Reference refer to the average thickness of cited layer or film, and adjacent layer may depend on certain material and be tangled in its boundary. In certain embodiments, overall membrane structure can have the total transmission of at least about 85% visible ray, be no more than about 2 percent Turbidity and no more than about 250ohm/sq sheet resistance upon formation, but considerably better performance described herein.

In order to be incorporated in the clear coat for nesa coating or be directly incorporated into for forming sparse metal conducting layer In ink, loaded external coating does not significantly increase sheet resistance generally, and in certain embodiments, sheet resistance is relative to right 20% should be no more than about without the sheet resistance increase of film carrier；In a further embodiment, sheet resistance increase is no more than about 15%；And in Additional examples of composition, sheet resistance increase no more than about 10%.For general optical application, external coating can The total transmittance reduction no more than about 5 of light is will be seen that without the percent value of the total transmission of film carrier relative to correspondence；In addition Embodiment in, it is seen that the total transmittance of light reduction no more than about 3；In Additional examples of composition, it is seen that the total transmittance reduction of light No more than about 2；And in other embodiments, it is seen that the total transmittance reduction no more than about 1 of light.Furthermore, it may be desirable to which turbidity is not It can roll up because of the filler in coating.In certain embodiments, by the turbidity unit being normally reported as percentage, turbidity Value can improve no more than about 0.5 without the turbidity value of film carrier relative to correspondence；In a further embodiment, turbidity value is improved not More than about 0.4；And in Additional examples of composition, turbidity value improves no more than about 0.3.In certain embodiments, turbidity can be reduced.Institute The those skilled in the art in category field are it will be recognized that the sheet resistance covered in clear and definite scope above is improved, total transmittance changes And the additional range that turbidity changes, and the scope is within the scope of the present invention.Have by other components in solvent identical dense The coating solution spent and processed in the same manner is produced with reference to without film carrier so that final thickness can be slightly different.

Having found can be via the integrally-built appropriately designed very effective stabilization for realizing sparse metal conducting layer.It is specific next Say, stable composition can be placed in the layer adjacent with sparse metallic conductive element (it can be external coating or priming coat).In addition, can Prepared, and had found for nesa coating is attached into device using optical clarity sticker (for example, being used as the component of film) The selection of optical clarity sticker remarkably promotes the stability for obtaining and wanting degree.Specifically, optical clarity sticker can be wrapped Include the double-sided adhesive layers in carrier layer.Carrier layer can be polyester (for example, PET or business abarrier layer material), and it can provide and want Moisture and gas potential barrier are to protect sparse metal conducting layer, but applicant is not intended to be grasped by the limpid sticker of particular optical Make the limitation of principle.

Nesa coating is widely used in such as solar cell and touch-screen.By metal nanometer line component formed it is saturating Bright conducting film provides the relatively low processing cost and the more prospect of the physical property of adaptability relative to traditional material.With each In the multilayer film for planting structural polymer layer, it has been found that gained membrane structure is firm in terms of processing, while maintaining to want conductance Rate, and want being incorporated to for component to provide stable without making the functionality of film degrade in addition as described in this article so that The suitable life-span can be had under normal usage by incorporating the device of the film.

Clear coat and film

The clear coat of polymer with loading nano-particle described herein is generally coated on for being incorporated to institute Want in the transparent substrates in structure.Describe general structure, and in sections below find nesa coating application-specific.Typically For, it appropriate coating method can be used to be deposited in transparent substrates to be formed for the transparent precursor solution for being filled through coating Transparent configuration.In certain embodiments, transparent substrates can be for being incorporated to resulting device or alternately or in addition incorporated light Learn the film in component (for example, light-emitting device or optical pickup apparatus).Discussion concentrates on simple passive state transparent substrates and then phase Should ground discussion other structures.

In general, any rational transparent substrates can be what is be adapted to.Therefore, can be by (such as) unorganic glass (for example, silicon Silicate glass), transparent polymer film, mineral crystal or its analog form suitable substrate.In certain embodiments, substrate is Polymer film.For substrate suitable polymer including (for example)：Poly terephthalic acid stretches ethyl ester (PET), poly- naphthalenedicarboxylic acid Stretch ethyl ester (PEN), polyacrylate, poly- (methyl methacrylate), polyolefin, polyvinyl chloride, fluoropolymer, polyamide, poly- Acid imide, polysulfones, silicone alkane, polyether-ether-ketone, polynorbornene, polyester, polystyrene, polyurethane, polyvinyl alcohol, poly- acetic acid second Alkene ester, acrylonitrile butadient styrene, cyclic olefin polymer, cyclic olefin copolymer, makrolon, its copolymer or Its admixture or its analog.Fluoropolymer is including (for example) polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), hexafluoro third Alkene, perfluoropropyl vinyl ether, perfluorinated methyl ethylene ether, polychlorotrifluoroethylene and the like.Polymerization for some embodiments Thing film can have from about 5 microns to about 5mm thickness；In a further embodiment, with from about 10 microns to about 2mm thickness Degree；And in Additional examples of composition, with from about 15 microns to about 1mm thickness.One of ordinary skill in the art will recognize that Arrive, cover the additional thickness scope in above-mentioned clear and definite scope, and the scope is within the scope of the present invention.Substrate may include by group Into and/or other character distinctions multiple layers.The particularly scope of the applicable material of substrate for nesa coating is below It is middle to present, and general substrate scope will include these certain materials and property.Suitable polymer for coating can include (example Such as) radiation curable polymer and/or thermal curable polymer, such as polyurethane, acrylic resin, acrylic copolymer Thing, cellulose ether and cellulose esters, other structures polysaccharide, polyethers, polyester, the polymer containing epoxy radicals, its copolymer and its Mixture.

The clear coat for strengthening nanoparticulate fillers with property could generally have no more than about 25 microns of thickness；Another In outer embodiment, with from about 20 nanometers (nm) to about 10 microns of thickness；In other embodiments, with from about 35nm to About 5 microns of thickness；And in Additional examples of composition, with the thickness from about 50nm to about 2 micron.By the poly- of loading nano-particle The clear coat of compound formation may include to strengthen nano-particle from about 0.01 weight % (wt%) to about 70wt% property；Another In outer embodiment, it may include strengthen nano-particle from about 0.05wt% to about 60wt% property；In other embodiments, may be used Including strengthening nano-particle from about 0.1wt% to about 50wt% property；And in Additional examples of composition, it may include from about 0.2wt% to about 40wt% property enhancing nano-particle.Clear coat can further comprise being used for nesa coating and optional The polymer adhesive of the sparse metal conducting layer in ground, optional property modification agent (for example, crosslinking agent, wetting agent, viscosity modification agent) And/or stabilizer (for example, antioxidant and/or UV stabilizer).One of ordinary skill in the art are it will be recognized that cover The thickness and the additional range of nanoparticle concentration of loaded polymer in clear and definite scope, and the scope is in the present invention above In the range of.

Strengthen nano-particle on property, Nano diamond is presented especially with respect to hardness and thermal conductivity and to a certain degree On desired properties on dielectric constant.Both hardness and thermal conductivity of block diamond all occupy the prostatitis of known materials.So And, additional materials provide being worth for these properties.For convenience, although nanoparticle properties generally generally directly reflect Block property, but because the value of nano-particle can be more difficult to get, therefore reference pair answers the material character of block materials.Property strengthens The carbon material that the material of nano-particle is usually inorganic material or wherein most material is elemental carbon, it is for example known as fowler Alkene, 3-dimensional crystal (diamond), 2 dimension crystal (graphitic carbon), amorphous form (for example, carbon black) and the like.Nano-particle can With surfaction, comprising organic surfaction, the identification without changing the nano-particle according to most of core material.

For related material, the hardness of block materials refers to Vickers hardness measurement.Vickers hardness is to press material Measurement.ASTM E384 and ISO 6507-1-2005 (can be included, both of which is herein incorporated by reference by the recognized standard Vickers hardness is measured herein).List illustrates the Vickers hardness of many materials of interest.Vickers hardness is generally with HV (dimensions Family name's pyramid numerical value, kilogram/square millimeter (kg-force/mm²)) reported for unit, but it can be reported in units of Pascal Accuse, even if it is actually and non-pressure.In certain embodiments, can have at least about corresponding to the block materials of nano-particle 1650HV Vickers hardness；In certain embodiments, there can be at least about 1750HV Vickers hardness；And in Additional examples of composition In, there can be at least about 1800HV Vickers hardness.In addition to Nano diamond, the extra hard of nano-particle is strengthened for property Material is also including (for example) boron nitride, B₄C, cube BC₂N, carborundum, tungsten carbide, aluminium boride, crystallization alpha-aluminium oxide (sapphire) or Its analog.

On high thermal conductivity material, suitable material can have at least about 30W/ (mK) block thermal conductivity；In addition Embodiment in, the block thermal conductivity with least about 35W/ (mK)；And in certain embodiments, with least about 50W/ (mK) block thermal conductivity.One of ordinary skill in the art are it will be recognized that cover the thermal conductivity in above-mentioned clear and definite scope The additional range of the rate and scope is within the scope of the present invention.Suitable high thermal conductivity material is also included in addition to Nano diamond (for example) many metal elements (unionization element morphology) and metal alloy, graphene, silicon nitride, boron nitride, aluminium nitride, arsenic Change gallium, indium phosphide, aluminum oxide and its mixture.On high-k, various titanates have high-k, such as metatitanic acid Barium, strontium titanates, lead titanates, lead zirconium titanate, CaCu 3 Ti 4 O and its mixture.

Related nano-particle is usually commercially available.Nano-particle source is limited including (for example) American Studies nano material Company's (Texas, USA), it sells many materials of interest；Byk Chemie GmbH (Germany)；Austria of Sigma is auspicious Very (Missouri, USA)；Nano-structured and non-crystalline material (Texas, USA)；Sky Spring nano materials are limited Company's (Texas, USA)；And nanometer technology company (Illinois, America Luo Miouweier cities (Romeoville, Illinois)).In addition, laser pyrolysis technology has been developed for the synthesis of broad range of dispersed nano-particle, such as finish Et al. (Bi) entitled " powder coating and counter structure (the Nanoparticle-Based Powder based on nano-particle Coatings and Corresponding Structures) " United States Patent (USP) 7, described in 384,680, the patent with The mode of reference is incorporated herein.

Nano diamond or diamond nano particle generally can be natural nano diamond or synthesizing nano diamond, and receive Rice diamond particles may include by the circular crystallization Nano diamond core of the shell of graphite and/or amorphous carbon.It is attributable to spy The surface for processing (for example, functionalisation of surfaces) and forming Nano diamond is synthesized after determining synthetic method and being optional.For business Using suitable diamond nano particle is usually synthesizing nano diamond, and it is commercially available.The surface of Nano diamond can The functionalized chemical property to influence Nano diamond, such as dispersibility and/or compatible with particular polymers adhesive Property.The average diameter of nanodiamond particle generally can be no more than about 100nm；In a further embodiment, be from about 2nm to About 75nm；And be from about 2.5nm to about 50nm in Additional examples of composition.One of ordinary skill in the art are it will be recognized that contain The additional range and the scope for the Nano diamond average diameter covered in above-mentioned clear and definite scope are within the scope of the present invention.

If synthesizing nano diamond can be produced by drying method.For example, gas phase formation (for example, chemical vapor deposition), The ionizing radiation of graphite, the chlorination of carbide and the technology using shock wave energy are the generation diamond particles or thin nanometer Some in some possible ways of diamond film.In addition to the diamond nano particle of rough spherical morphology, other 1 have been manufactured Dimension and 2 dimension nano diamond structures, such as Nano diamond rod, thin slice, piece and the like, it can be additionally used in UV protection combinations (the method on synthesizing these structures, referring to O. Shen Denuowa (O.Shenderova) and G. Mikes Kui Er in thing (G.McGuire) " Types of Nanodiamonds " chapters and sections " Ultrananocrystalline diamond: Synthesis, Properties and Applications ", editor：O. Shen Denuowa, D. Ge Luen (D.Gruen), prestige Honest and clean-Theresa Andrews publishing house, 2006, the content of the book is incorporated herein by reference).Business nanodiamond particle Generally formed by controlled explosion technology, be for example described in Wa Ruisichajin (Vereschagin) et al. it is entitled " diamond- Carbon material and its production method (Diamond-Carbon Material and Method for Producing Thereof) " United States Patent (USP) 5,916,955 in technology, the patent is incorporated herein by reference.For the Nano diamond that explodes Improved purification process be described in (such as) Dorr Ma Tuofu (Dolmatov) et al. it is entitled " blast Nano diamond material Purification process and products thereof (Detonation Nanodiamond Material Purification Method and Product Thereof) " the PCT application case WO 2013/135305 through announcement in, the application case is by reference simultaneously Enter herein.Can be from nano-sized carbon research with various surface chemical properties or the business Nano diamond being scattered in various solvents Co., Ltd of institute (Japan)；PlasmaChem (Germany)；Carbodeon Co., Ltds (Finland)；NEOMOND (South Korea)；Western lattice Ma Aoruiqi (U.S.) and ray technology Co., Ltd (Israel) buy.

Nanodiamond particle each generally includes mechanically stable, chemical inertness crystallization nuclei and is typically considered to relative With chemically active surface.By using target substance functionalization nano diamond particle surface, Nano diamond can possess through The chemistry and/or physical property of modification.Functionalization can be completed so that difference to be had by various chemistry, photochemistry and electrochemical method Machine functional group is grafted on Nano diamond.Physical property and application are wanted depending on Nano diamond, functionalized receives Rice diamond can for fluorination, chlorination, carboxylation, amination, it is hydroxylated, hydrogenation, sulfonation or its mixture. Entitled referring to (such as) Yao (Yao) " is used for technique (the Process for for producing the dispersion liquid of fluorinated nano diamond Production of Dispersion of Fluorinated Nano Diamond) " the U.S. Patent application through announcement Case 2011/0232199 and (carboxylation Nano diamond) Malian subunitEt al. entitled " be used to produce ξ negativity nanometer Method and ξ negativity nanodiamond liquid dispersion (the A Method for Producing Zeta of diamond dispersion liquid Negative Nanodiamond Dispersion and Zeta Negative Nanodiamond Dispersion) " PCT application case WO 2014/174150 through announcement, the application case is incorporated herein by reference.Functionalization and/or Purifying removes and/or broken nano-particle coalescence available for help.In general, business Nano diamond do not coalesce fully with For being processed into relatively uniform film as described in this article.PH, concentration, solvent and the other dispersion properties of solution can be through Adjustment is with further aid dispersion Nano diamond.For example, carboxylation Nano diamond is generally stably scattered in higher pH In solution, and hydrogenation and amination Nano diamond are generally stably scattered in compared with low ph solution.

The hardness of loaded polymer film can be measured by the pencil hardness test for film based on ASTM D3363. After pencil sharpening method, using the constant power being downwardly applied to while making pencil keep 45° angle.For measurement using 500 grams or 750 grams of pencil hardness external member.Determined by analyzing influence of the pencil of different graphite step scales to base conductive layer hard Degree.If not damaging basic unit, then think that the film is qualified.Examined below Lycra (Leica) microscope with 20x magnifying powers Look into the film.The scope of hardness scale(degree) is grade point 9B to 9H, wherein B high value corresponding to relatively low hardness number, and H compared with Big value corresponds to the hardness through raising, and F value connection B and H scopes, and minimum " B " value is HB, is afterwards B, 2B ..., 9B. In some embodiments, relative to whole other sides it is equivalent but without property strengthen nano-particle coating, with property increase The coating of strong nano-particle can have the pencil hardness of at least one high hardness level；In certain embodiments, with high at least The pencil hardness of about two grades；And in a further embodiment, the pencil hardness with up at least about Three Estate.For hard Other scales of degree and test are available, and will comply with trend similar in nature.Also table is abutted against by using 100g weight Face rub steel wool and assess Scratch Resistance, further described in such as following instance.Will be ultra-fine after coating clear topcoat Steel wool is used to scrape the film by friction surface.

Transparent loaded coating can be formed by using appropriate coating method coating precursor solution.Property strengthens nanometer Particle and/or stable composition are incorporated into selected suitable solvent to deposit the coating with appropriate compatibility.It is adapted to Solvent generally comprises (such as) water, alcohol, ketone, ester, ether (for example, glycol ethers), aromatic compounds, alkane and the like and its mixed Compound.Specific solvent including (for example) water, ethanol, isopropanol, isobutanol, the tert-butyl alcohol, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Cyclic ketone (for example, cyclopentanone and cyclohexanone), glycol ethers, toluene, hexane, ethyl acetate, butyl acetate, ethyl lactate, carbonic acid Propylene diester, dimethyl carbonate, PGMEA (acetic acid 2- methoxyl group -1- Methylethyls ester), N,N-dimethylformamide, N, N- diformazans Yl acetamide, acetonitrile, formic acid or its mixture.

In general, usually the polymer for coating of crosslinkable polymer can be supplied as business coating composition Should, or allocated by selected polymer composition.It is adapted to radiation curable polymer and/or the heat solidifiable polymerization of classification Thing including (for example) silicone alkane, polysilsesquioxane, polyurethane, acrylic resin, acrylic acid series copolymer, cellulose ether and Cellulose esters, nitrocellulose, other structural polysaccharides for being insoluble in water, polyethers, polyester, polystyrene, polyimides, fluorine gather Compound, styrene-acrylic copolymer, styrene-butadiene-copolymer, acrylonitrile butadient styrene, polysulfide Thing, the polymer containing epoxy radicals, its copolymer and its mixture.Suitable commercial coating compositions including (for example)：Come from The coating solution of Di Ruihe companies (Japan)；From mixed plastic Co., Ltd (Mississippi, America)Coating； Silica filled silicon coating from California hard conating company (California, USA)；From SDC technologies The crystal coating UV curable coating of Co., Ltd's (California, USA).Polymer concentration and accordingly it is other it is non-easily The concentration of the property lost agent can be chosen to reach the rheological equationm of state of wanting of coating solution, such as the suitable of selected coating process Work as viscosity.Solvent can be added or remove to adjust total solid concentration.The relative quantity of solid may be selected to adjust finished product coating compositions The composition of thing, and the total amount of adjustable solid wants thickness to reach through dry coating.In general, coating solution can have From about 0.025wt% to about 50wt% polymer concentration；In a further embodiment, with from about 0.05wt% to about 25wt% polymer concentration；And in Additional examples of composition, with from about 0.075wt% to about 20wt% polymer concentration. One of ordinary skill in the art should be understood that the additional range for covering the polymer concentration in above-mentioned particular range and institute State scope within the scope of the present invention.

Property enhancing nano-particle is incorporated into for being formed in the coating solution of coating.Coating precursor solution may include From about 0.005wt% to about 5wt% nano-particle；In a further embodiment, it may include from about 0.01wt% to about 3wt% Nano-particle；And in Additional examples of composition, it may include strengthen nano-particle from about 0.025wt% to about 2wt% property.Institute The those skilled in the art in category field are it will be recognized that cover the property enhancing nanoparticle in the coating solution in clear and definite scope above The additional range and the scope of son are within the scope of the present invention.Additional additive can be added on demand (for example, wetting agent, viscosity Modification agent, dispersing aid and the like).

In certain embodiments, relative to the corresponding coating of nano-particle is strengthened without property, nanometer is strengthened with property The clear coat of particle can cause the total transmittance of visible ray to reduce no more than about 5 percentage points；In a further embodiment, do not surpass Cross about 3 percentage points；And in Additional examples of composition, no more than about 1.5 percentage points.In addition, in certain embodiments, relative to correspondence Unloaded coating, the clear coat for strengthening nano-particle with property can cause turbidity to improve no more than about 1.5 percentage points；Another In outer embodiment, no more than about 1 percentage point；And in Additional examples of composition, no more than about 0.6 percentage point.The one of art As it will be recognized that covering the volume of the optical property for being attributed to loaded polymer coating above in clear and definite scope It is outer modification scope and the scope within the scope of the present invention.In addition to non-existent nano-particle, correspondence unloaded coating is molten There are same concentrations in agent and process in the same manner so that the final thickness of coating can somewhat different than corresponding coating.

For the deposition of coating precursor solution, any rational deposition process, such as dip-coating, spraying, the edge of a knife can be used Coating, rod painting, Mel bar (Meyer-rod) coating, slit die coating, intaglio printing, spin coating or its similar approach.Deposition side Method controls the amount of deposited liquid, and the concentration of solution may be adjusted to provide the product coating of wanted thickness on the surface. After by dispersion liquid formation coating, coating can remove liquid and suitably be crosslinked through drying.

Nesa coating

Transparent conducting structures or film are generally included：Sparse metal conducting layer, it provides electrical conductivity without significantly, adversely Change optical property；And various additional layers, it provides the mechanical support and protection to conducting element.In general, polymer External coating is placed in above sparse metal conducting layer.Property enhancing nano-particle as described in this article can be placed in external coating, In optional priming coat and/or it is placed directly within sparse metal conducting layer.Sparse metal conducting layer it is very thin and accordingly easily by by The infringement that mechanical and other abuses are caused.Property enhancing nano-particle can provide some type of protection, and as in previous section Described, other elements of stable compound and film can provide Additional Protection.On the susceptibility to environmental nuisance, it has been found that Priming coat and/or external coating may include that claimed stable composition, and the optical clarity sticker of some classifications can be provided And/or barrier layer may also provide to light, heat, chemical substance and the valuable protection of other environmental nuisances.Although concern herein From humid air, heat and light environmental assaults, but for prevent conductive layer by these environmental assaults polymer flake also It can provide and dock tactile and the like protection.

Therefore, sparse metal conducting layer can be formed on substrate, can have one or more layers in the structure of the substrate. Substrate generally can be identified as self-supported membrane or flake structure.Thin solution machined layer referred to as priming coat can be optionally along lining The top surface of counterdie and placed close to below sparse metal conducting layer.In addition, sparse metal conducting layer can be coated with additional layer, The layer provides certain protection on the side opposite with substrate of sparse metal conducting layer.In general, conductive structure can be most It is placed in finished product in any orientation, i.e. substrate faces outwardly the surface that substrate abuts against the support conductive structure of product.One In a little embodiments, multiple coatings (i.e. priming coat and external coating) can be coated, and each layer can be enhanced with correspondence property is used for Chosen additive.

With reference to Fig. 1, representative transparent conducting film 100 includes substrate 102, priming coat 104, sparse metal conducting layer 106, outer Coating 108, optical clarity adhesive linkage 110 and protectiveness superficial layer 112, although simultaneously not all embodiments includes all layers.Tool For body, coiled nesa coating can be distributed as top layers together with external coating, for post-processing, (it may or may not It is related to and then adds extra overlying strata).In these embodiments, for the risk for being reduced by the infringement to conducting film, with machine Hard external coating can be desirable on tool.Nesa coating generally includes sparse metal conducting layer and led in sparse metal At least one layer on every side of electric layer.In certain embodiments, the gross thickness of nesa coating can have from 5 microns to about The thickness of 3 millimeters (mm)；In a further embodiment, can have from about 10 microns to about 2.5mm thickness；And implement other In example, can have from about 15 microns to about 1.5mm thickness.One of ordinary skill in the art are it will be recognized that cover upper State the additional range and the scope of thickness in true scope clearly within the scope of the present invention.In certain embodiments, it may be selected such as The length and width of produced film are further added with being suitable for application-specific with causing the film to be introduced directly into Work is into product.In extra or alternate embodiment, the width of film may be selected for application-specific, and the length of film can be long (wherein it is expected that the film can be through being cut into the desired length for using).For example, the film can be in sliver or scroll Formula.Similarly, in certain embodiments, film can in rolls or in another large-scale reference format, and the film element can according to In the desired length and width used and cutting.

Substrate 102 generally includes the durable supporting layer formed by one or more appropriate polymer.In some embodiments In, substrate can have from about 10 microns to about 1.5mm thickness；In a further embodiment, can have from about 15 microns to about 1.25mm thickness；And in Additional examples of composition, can have from about 20 microns to about 1mm thickness.The general skill of art Art personnel are it will be recognized that cover the additional range and the scope of the substrate thickness in above-mentioned clear and definite scope in the scope of the invention It is interior.Suitable optical clarity polymer with excellent clarity, low turbidity and good protection ability can be used for substrate.Suitable Polymer including (for example) poly terephthalic acid stretch ethyl ester (PET), poly- naphthalenedicarboxylic acid stretch ethyl ester (PEN), it is polyacrylate, poly- (methyl methacrylate), polyolefin, polyvinyl chloride, fluoropolymer, polyamide, polyimides, polysulfones, silicone alkane, polyethers ether Ketone, polynorbornene, polyester, polystyrene, polyurethane, polyvinyl alcohol, polyvinyl acetate, acronitrile-butadiene-styrene are common Polymers, cyclic olefin polymer, cyclic olefin copolymer, makrolon, its copolymer or its admixture or its analog.Suitable Commercial polycarbonates substrate including (for example)：MAKROFOL SR243 1-1CG, are purchased from Bayer (Bayer) material science public Department；Plastics, are purchased from TAP Plastics Companies；And LEXAN^TM8010CDE, is purchased from SABIC innovation Plastics Companies.Protection Property superficial layer 112 can independently have covering and this section of substrate identical thickness range and compositing range described above Thickness and composition.

Can be selected independently with comprising optional priming coat 104 and/or optional external coating 108 can be respectively placed in sparse metal The below or above of conductive layer 106.Optional coating 104,108 may include curable polymer, and such as heat solidifiable or radiation can be consolidated Fluidized polymer.Suitable polymer for coating 104,108 is described below as to contain in metal nanometer line Adhesive in ink；And the list of polymer, corresponding crosslinking agent and additive be equally applicable to optional coating 104,108 and Without clearly repeating to discuss herein.Coating 104,108 can have the thickness from about 25nm to about 2 micron；In other implementation In example, there can be the thickness from about 40nm to about 1.5 micron；And in Additional examples of composition, can have from about 50nm to about 1 micron Thickness.One of ordinary skill in the art are it will be recognized that cover the extra of the external coating thickness in above-mentioned clear and definite scope The scope and scope is within the scope of the present invention.In general, the small thickness of external coating 108 allows via the conduction of external coating 108, So that sparse metal conducting layer 106 is may be electrically connected to, but in certain embodiments, external coating may include sublayer, wherein via one A little layer but not necessarily via all sublayers provide electrical conductivity.

Optional optical clarity adhesive linkage 110 can have the thickness from about 10 microns to about 300 microns；In further embodiment In, there can be the thickness from about 15 microns to about 250 microns；And in other embodiments, can have from about 20 microns to about 200 The thickness of micron.One of ordinary skill in the art are it will be recognized that cover the optical clarity bonding in above-mentioned clear and definite scope The additional range and the scope of the thickness of layer are within the scope of the present invention.Suitable optical clarity sticker can be contact adhesion Agent.Optical clarity sticker is including (for example) can coating composition and adhesive tape.It can obtain based on acrylic acid series or silicone alkanisation The UV curable liquid optical clarity stickers of property.Suitable adhesive tape is commercially available, such as purchased from Japanese Lin get Ke companies (MO series)；Saint Gobain Performance Plastics (DF713 series)；Nitto Americas(Nitto Denko) (LUCIACS CS9621T and LUCIAS CS9622T)；(DAITAC LT series OCA, DAITAC WS systems of DIC companies Arrange OCA and DAITAC ZB series)；PANAC plastic foils company (PANACLEAN series)；Minnesota mining industry and manufacturing company (3M, Minn.-production code member 8146,8171,8172,8173, and similar products)；And adhesive research (for example, Product 8932).

Amount for the nano wire being delivered on substrate of sparse metal conducting layer 106 can relate to the balance of factor to reach The transparency and electrical conductivity of the desired amount.Although the thickness of nanometer line network scanning electron microscopy can be used to assess in principle, Network can be relatively sparse to provide optical clarity, and it can complicate measurement.In general, sparse metallic conductive element (example Such as, molten metal nanometer line network) by with no more than about 5 microns of average thickness；In a further embodiment, no more than about 2 microns；And be from about 10nm to about 500nm in other embodiments.However, sparse metallic conductive element is usually opened relatively Opening structure, the obvious surface texture with submicron-scale.The useful load of nano wire can provide the useful network that can be easy to assess Parameter, and loading values provide the alternate parameter related to thickness.Therefore, as used herein, dress of the nano wire on substrate Carrying capacity is typically rendered as the milligram quantities of nano wire in one square metre of substrate.In general, metallic conduction network is (in spite of molten Melt) can have from about 0.1 milligram of (mg)/m²To about 300mg/m²Loading；In a further embodiment, it is from about 0.5mg/m² To about 200mg/m²；And be from about 1mg/m in other embodiments²To about 150mg/m².In conductive network, transparency conducting layer It may include the metal from about 0.5wt% to about 70wt%；In other embodiments, it is from about 0.75wt% to about 60wt%；And In a further embodiment, it is metal from about 1wt% to about 50wt%.One of ordinary skill in the art it will be recognized that Cover additional range and the scope that thickness in above-mentioned clear and definite scope and metal load within the scope of the present invention.If dilute Dredge metal conducting layer patterned, then thickness and loading discussion are only applicable to metal not because Patternized technique is excluded or is shown Write reduced region.In addition to polymer adhesive and other processing aids and the like, sparse metal conducting layer can also be wrapped Include property enhancing nano-particle.Strengthen the concentration of nano-particle above with respect to the property described by the loading in transparent polymeric layer Scope be generally also applied to sparse metal conducting layer.

In general, in the range of the general thickness of the specific components above for film 100, layer 102,104,106,108, 110th, 112 sublayer can be separated into, such as with the composition different from other sublayers.For example, external coating may include have not Congeniality strengthens the sublayer of component.In certain embodiments, sublayer is coated with outside top may include high dielectric nanoparticles, and it can press down Make the conduction via the layer.Then outer coating sublayer can be not necessarily penetrated via the top sub-layer for penetrating external coating 108 Window, metal tags or its analog (it may include (such as) Nano diamond and/or stable composition) set up electrical connection.This Outside, multiple layers of optical clarity sticker are discussed above.Therefore, more complicated layer stack can be formed.It can be similar in certain layer Other sublayers or can not be similar to certain layer in other sublayers process sublayer, such as one sublayer can be laminated and another Sublayer can coated and solidification.

Stable composition can be placed in appropriate layer to stablize sparse metal conducting layer.Include for sparse metal conducting layer The embodiment of nanostructured metal network is melted, the sparse metal conducting layer itself formed may not include stable compound, this It is due to that the presence of these compounds can suppress chemical melting process.In alternative embodiments, led for forming sparse metal It can be acceptable that stabilizer is included in the coating solution of electric layer.Similarly, stable compound may be included in optical clarity adhesion In agent composition.However it has been found that stable compound effectively can be contained in coating, it can accordingly cause that the coating is relative It is thin to stablize while being still provided with effect.Specific description with the coating for stablizing composition is described in previous section.Due to tool The layer for having stable composition can be thin, therefore can obtain to be stablized by low stabilizer total amount, and this comes from machining angle Say can be desirable and with the low influence on optical property.

For some applications, it is necessary to make the current-carrying part of film pattern to introduce wanted functionality, such as touch sensor Different zones.Can be loaded by changing the metal on substrate surface (by the type metal nano wire at chosen position, And other positions are practically without metal, or before melting nano wire and/or afterwards from chosen position etching or with it Its mode degrades metal) perform patterning.However it has been found that can be in the case where being loaded with substantially equivalent metal in layer Melting and the high-contrast of electrical conductivity is not realized between puddle so that can be held by optionally molten metal nano wire Row patterning.This ability patterned based on melting is provided the selectivity based on nano wire and melted (for example, via choosing Selecting property delivers melt solution or steam) important additional patterned option.The pattern of selectivity melting based on metal nanometer line In the change application case of ' 833 described above and the application case of ' 380.

As illustrative example, molten metal nanostructured network can form conductive pattern along substrate surface 120, wherein Multiple conductive paths 122,124 and 126 are surround by resistive region 128,130,132,134, as shown in Figure 2.Such as institute in Fig. 2 Show, melting zone and three different conductive regions corresponding to conductive path 122,124 and 126 are corresponding.Although in fig. 2 Illustrate the conductive region of three independent connection, it should be appreciated that can form only with two, four or more than four conductions on demand Vertical conductive path or the pattern in region.For many business applications, the quite complicated figure with a large amount of elements can be formed Case.Specifically, by the available patterning techniques suitable for patterning film described herein, it can be formed with high score The very fine pattern of resolution feature.Similarly, the shape in particular conductivity region can be selected on demand.

Nesa coating is typically established at sparse metallic conductive element (its deposited functionality feature to form film) week Enclose.Various layers are coated with to, be laminated or are otherwise added to structure using appropriate film processing method.As retouched herein State, the property of layer can significantly change the long-term behaviour of nesa coating.Further molten metal nanostructured layers below is upper The deposition of sparse metal conducting layer described in hereafter, but non-molten metal nano wire coating can it is similarly deposited (only not There is molten component).

Sparse metal conducting layer, in substrate, may or may not have then generally by solution coating on the top of the substrate Form the coating of the priming coat adjacent to sparse metal conducting layer.In certain embodiments, external coating can be by solution coating in dilute Dredge on metal conducting layer.It is executable to pass through application UV light, the crosslinking of hot or other radiation so that coating and/or sparse metallic conduction Polymer adhesive crosslinking in layer, this can be with a step or execution of multiple steps.

Sparse metal conducting layer

Sparse metal conducting layer is generally formed by metal nanometer line.It is linear by enough loadings and chosen nanometer Matter, can realize rational electrical conductivity by the nano wire with the appropriate optical property of correspondence.It is expected that described herein steady Performance can be wanted for the film generation with various sparse metallic conduction structures by determining membrane structure.However, being received by molten metal Rice structural network reaches especially desired properties.

It is as outlined above, some practical approaches have been developed to realize that metal nanometer line is melted.Can budget metals loading To reach the electrical conductivity and good optical properties of wanted level.In general, metal nanometer line processing can be two kinds via deposition Ink (wherein the first ink, which includes metal nanometer line and the second ink, includes melt composition), or via deposition by melting element The ink being combined in metal nanometer line dispersion liquid is realized.Ink may or may not further comprise additional processing auxiliary agent, adhesive Or its analog.Suitable patterning method may be selected with suitable for particular ink system.

In general, can jointly it include well for forming one or more solution or ink of metal Nano structure network Metal nanometer line, melting agent and optional additional component that ground disperses, such as polymer adhesive, crosslinking agent, wetting agent (such as boundary Face activating agent), thickener, dispersant, other optional additives or its combination.It is molten for metal nanometer line ink and/or melting The solvent of liquid (if different from nano wire ink) may include aqueous solvent, organic solvent or its mixture.Specifically, it is adapted to Solvent including (for example) water, alcohol, ketone, ester, ether (for example, glycol ethers), aromatic compounds, alkane and the like and its mixing Thing.Specific solvent is including (for example) water, ethanol, isopropanol, isobutanol, the tert-butyl alcohol, methyl ethyl ketone, glycol ethers, methyl tert-butyl Base ketone, toluene, hexane, ethyl acetate, butyl acetate, ethyl lactate, PGMEA (acetic acid 2- methoxyl group -1- Methylethyls ester) or Its mixture.Although should based on formed metal nanometer line fine dispersion liquid ability select solvent, solvent should also with it is other Selected additive is compatible to cause additive to dissolve in solvent.Single solution is contained in for melting agent and metal nanometer line In embodiment, solvent or its component may or may not for melt solution notable component (for example, alcohol) and if necessary to so may be used Correspondingly select.

The metal nanometer line ink configured in single ink or double inks can be received comprising from about 0.01 to about 1 weight % metal Rice noodles；In a further embodiment, from about 0.02 to about 0.75 weight % metal nanometer line can be included；And in Additional examples of composition In, from about 0.04 to about 0.5 weight % metal nanometer line can be included.One of ordinary skill in the art should be understood that culvert The additional range and the scope for the metal nanometer line concentration covered in above-mentioned clear and definite scope are within the scope of the present invention.Metal nano The physical property of metal loading and ink on the concentration influence substrate surface of line.

In general, nano wire can be formed by a series of metals, for example silver, gold, indium, tin, iron, cobalt, platinum, palladium, nickel, cobalt, Titanium, copper and its alloy, it can be desirable that it, which is attributed to high conductivity,.Commercial metals nano wire is purchased from Sigma Ao Ruiqi (Missouri, USA), Cangzhou nanochannel materials Co., Ltd (China), Blue Nano (North Carolina), EMFUTUR (Spain), sea cowry shell technology (California, USA), Chinese mugwort step on (South Korea), nanoComposix (U.S.), Nanopyxis (South Korea), K＆B (South Korea), ACS materials (China), Kechuang advanced material (China) and Nanotrons (U.S.). Silver especially provides splendid electrical conductivity, and business nano silver wire is obtainable.Or, it is also possible to use various known route of synthesis or Its version synthesis of silver nano-wire.In order to which with good transparency and low turbidity, nano wire is needed with a series of minor diameters. Specifically, metal nanometer line needs have no more than about 250nm average diameter；In a further embodiment, no more than about 150nm；And in other embodiments, from about 10nm to about 120nm.On average length, it is contemplated that the nanometer with long length Line provides preferable electrical conductivity in network.In general, metal nanometer line can have at least 1 micron of average length；In addition Embodiment in, at least 2.5 microns；And in other embodiments, from about 5 microns to about 100 microns, but the improvement of future development Synthetic technology can make it possible longer nano wire.It may specify ratio of the aspect ratio for average length divided by average diameter, and In some embodiments, nano wire can have at least about 25 aspect ratio；In a further embodiment, be from about 50 to about 10, 000；And be from about 100 to about 2000 in Additional examples of composition.One of ordinary skill in the art are it will be recognized that cover The additional range and the scope of nanowire size in above-mentioned clear and definite scope are within the scope of the present invention.

Polymer adhesive and solvent are generally as one man selected so that polymer adhesive is soluble or dispersible in molten In agent.In appropriate embodiment, metal nanometer line ink generally includes the bonding from about 0.02 weight % to about 5 weight % Agent；In a further embodiment, including from about 0.05 weight % to about 4 weight % adhesive；And in Additional examples of composition, bag Include the polymer adhesive from about 0.1 weight % to about 2.5 weight %.In certain embodiments, polymer adhesive include can Organic cross-linked polymeric thing, such as radiation cross-linkable organic polymer and/or heat solidifiable organic bond.To promote adhesive Crosslinking, in certain embodiments, metal nanometer line ink may include the crosslinking agent from about 0.0005wt% to about 1wt%；Another It is from about 0.002wt% to about 0.5wt% in outer embodiment；And be from about 0.005wt% to about in Additional examples of composition 0.25wt%.Nano wire ink can optionally include rheology modifying agent or its combination.In certain embodiments, ink may include wet Profit agent or interfacial agent are to reduce surface tension, and wetting agent is applicable to improve coating performance.Wetting agent is usually soluble in Solvent.In certain embodiments, nano wire ink may include the wetting agent from about 0.01 weight % to about 1 weight %；In addition Embodiment in, be from about 0.02 weight % to about 0.75 weight %；And in other embodiments, be from about 0.03 weight % to About 0.6 weight % wetting agent.Thickener can be optionally as rheology modifying agent is with stable dispersions and reduces or eliminates sedimentation. In certain embodiments, nano wire ink optionally can include from about 0.05 weight % to about 5 weight % thickener；In addition Embodiment in, be from about 0.075 weight % to about 4 weight %；And be from about 0.1 weight % to about 3 in other embodiments Weight % thickener.One of ordinary skill in the art should be understood that the adhesive covered in above-mentioned clear and definite scope, wet The additional range and the scope of profit agent and thickener concentration are within the scope of the present invention.

A series of polymer adhesives may be adapted to dissolution/dispersion in the solvent of metal nanometer line, and suitable adhesive Include the polymer developed for coating application.Hard conating polymer (for example, radiation-curable coating) is commercially available, example Such as can be chosen for being dissolved in a series of hard coat material for applications in aqueous or non-aqueous solvent.It is adapted to The radiation curable polymer and/or thermal curable polymer of classification are including (for example) silicone alkane, polysilsesquioxane, poly- ammonia Ester, acrylic resin, acrylic acid series copolymer, cellulose ether and cellulose esters, nitrocellulose, other water that are insoluble in Structural polysaccharide, polyethers, polyester, polystyrene, polyimides, fluoropolymer, styrene-acrylic copolymer, styrene fourth two Alkene copolymer, acrylonitrile butadient styrene, polysulfide, the polymer containing epoxy radicals, its copolymer and its mixed Compound.The example of commercial polymer adhesive including (for example)Board acrylic resin (DMS profit health resin),Board acrylic acid series copolymer (BASF resin),Board acrylic resin (Lu Caite states Border),Board polyurethane (Lubrizol Advanced Materials Corporation), cellulose acetate-butyrate polymer (come from Eastman^TMChemical CAB brands), BAYHYDROL^TMBoard polyurethane dispersing liquid (Bayer Material Science company),Board polyurethane dispersing liquid (Qing Te Industrial Co., Ltd),Board polyvinyl butyral resin is (laughable Beautiful Co., Ltd of the U.S.), it is cellulose ether (for example, ethyl cellulose or hydroxypropyl methyl cellulose), other poly- based on polysaccharide Compound (for example, chitosan and pectin), synthetic polymer of similar polyvinyl acetate and the like.Polymer adhesive Can self-crosslinking, and/or it can be with light trigger or other cross-linking agents after exposure to radiation.In certain embodiments, Photocrosslinking agent can form free radical after exposure to radiation, and then free radical is based on radical polymerization mechanism and induces crosslinking Reaction.Suitable light trigger is including (for example) commercially available product, for exampleBoard (BASF), GENOCURE^TMBoard (Rui Ang u s companys) andBoard (double bond Chemical Co., Ltd.), its combination or its class Like thing.

Wetting agent can be used for improving the coatability of metal nanometer line ink and the quality of metal nanometer line dispersion liquid.Tool For body, wetting agent can reduce ink surface can with cause ink after coating on the surface fully diffusion.Wetting agent can For interfacial agent and/or dispersant.Interfacial agent is to play the class material that drop low-surface-energy is acted on, and interfacial agent The dissolubility of material can be improved.Interfacial agent generally contributes to the hydrophilic molecular moiety and hydrophobic molecule of its property Part.Commercially available broad range of interfacial agent, such as non-ionic surfactant, cation interfacial active agent, anion Interfacial agent, amphion interfacial agent.In certain embodiments, if the property associated with interfacial agent not into Problem, then the wetting agent (for example, dispersant) of non-interfacial agent is also known in art and can be efficiently modified ink Wetting power.Suitable business wetting agent is including (for example) COATOSIL^TMBoard epoxy functional silane oligomer (Momentum Performance Materials)、SILWET^TMBoard organic silicone interfacial agent (Momentum Performance Materials)、THETAWET^TMBoard chain non-ionic fluorine interfacial agent (ICT Industrial Co., Ltd), Board polymeric dispersant (air products Co., Ltd),Board polymeric dispersant (Lu Borun), XOANONS WE- D545 interfacial agents (Anhui Xoanons Chemical Co., Ltd.), EFKA^TMThe polymeric dispersants of PU 4009 (BASF), MASURF FP-815 CP, MASURF FS-910 (Mason's chemistry), NOVEC^TMFC-4430 and FC-4432 fluorination interfacial activities Agent (3M), its mixture and the like.

Thickener can be used for improving the steady of dispersion liquid by reducing or eliminating solid from the sedimentation of metal nanometer line ink It is qualitative.Thickener may or may not significantly change the viscosity or other fluid properties of ink.Suitable thickener to be commercially available and Including (for example) CRAYVALLAC^TMBoard modification urea (such as LA-100) (Cray Willie acrylic acid, the U.S.), polyacrylamide, THIXOL^TM53L boards acrylic thickener, COAPUR^TM 2025、COAPUR^TM 830W、COAPUR^TM 6050、COAPUR^TM XS71 (high Supreme Being Si Co., Ltd),Board modification urea (BYK additives), Acrysol DR 73, Acrysol RM- 995th, Acrysol RM-8W (Tao Shi coating), Aquaflow NHS-300, Aquaflow XLS-530 hydrophobicitys modification polyether extended Thick dose (Ya Shilan Co., Ltds), Borchi Gel L 75 N, Borchi Gel PW25 (OMG Borchers) and its similar Thing.

As mentioned above, it can further comprise that property strengthens nanoparticle for depositing the ink of sparse metal conducting layer Son.Suitable property enhancing nano-particle includes Nano diamond and other properties enhancing nano-particle material presented above Expect (it is specifically incorporated into this discussion).In addition, above in the context of coating summarize Nanoparticle Size scope and It is similarly incorporated herein.Forming the solution of sparse metal conducting layer may include the nanometer from about 0.001wt% to about 10wt% Particle；In a further embodiment, it is from about 0.002wt% to about 7wt%；And be from about in Additional examples of composition 0.005wt% to about 5wt% property enhancing nano-particle.One of ordinary skill in the art, which should be understood that, to be covered upper State the additional range and the scope of nanoparticle concentration in true scope clearly within the scope of the present invention.

Additional additive can be added into metal nanometer line ink, additive is generally each in no more than about 5 weight %'s Amount；In a further embodiment, to be no more than about 2 weight %；And in a further embodiment, to be no more than about 1 weight %.Its Its additive can including (for example) antioxidant, UV stabilizer, defoamer or antifoaming agents, antisettling agent, viscosity modification agent or Its similar additive.

As indicated above, the melting of metal nanometer line can be via various doses of realizations.It is being not intended to the situation of bound by theory Under, melting agent phase courier metal ion activity, and free energy seems the reduction in melting process.In certain embodiments, excessively Metal migration or growth can cause the degeneration of optical property, therefore balanced deflection can be made (generally via with reasonable controlled way Continue short time period) reach desired result to produce enough meltings, to obtain wanted electrical conductivity while maintaining to want optics Property.In certain embodiments, to improve the concentration of component the starting of melting process can be controlled via the partially dried of solution, And can (for example) via the flushing to metal level or more complete drying realize being quenched for melting process.Melting agent can be together with gold Category nano wire is collectively incorporated into single ink.Single ink solution can provide the suitable control to melting process.

In certain embodiments, using the technique of the sparse nano wire film of initial deposition, and deposit or do not deposit another ink Following process be by metal nanometer line be molten to conduction metal Nano structure network in prepare.Controlled exposure can be passed through The deposition of melting agent performs melting process in melting steam and/or via solution.Sparse metal conducting layer be generally formed in through On the substrate surface of selection.The nano wire film that is deposited is generally through drying to remove solvent.As described further below, processing can It is suitable for the patterning of film.

For the deposition of metal nanometer line ink, any rational deposition process, such as dip-coating, spraying, the edge of a knife can be used Coating, rod painting, the coating of Mel bar, slit die coating, intaglio printing, spin coating or its similar approach.Ink, which can have, is directed to institute Want the property suitably adjusted by additive of deposition process, such as viscosity.Similarly, deposition process controls the deposition of liquid Amount, and the concentration of ink may be adjusted to provide metal nanometer line being loaded on the surface.Applied by dispersion liquid formation After layer, sparse metal conducting layer can remove liquid through drying.

Film (for example) can be dried by heat gun, baking oven, thermolamp or its analog, but in certain embodiments can be through Air dried film can be desired.In certain embodiments, film can be heated to from about 50 DEG C to about 150 DEG C during drying Temperature.After drying, film (for example) can be washed by alcohol or other solvents or solvent blends (for example, ethanol or isopropanol) One or more times turbidity is reduced to remove Excess solid.Patterning can be reached in some convenient modes.For example, metal is received The printing of rice noodles can directly result in patterning.Additionally or alternatively, lithographic techniques can be used for removing gold before melting or afterwards Belong to the part of nano wire to form pattern.

The clear diaphragm for covering sparse metal conducting layer can be formed and in position in there is hole or its is similar Thing, to provide the electrical connection to conductive layer.In general, various polymer film process technologies and equipment can be used for these polymer The processing of thin slice, and the equipment and technology are very complete in the art, and the process technology and equipment of following exploitation can It is suitably adapted for material herein.

Hyaline membrane electrical property and optical property

Molten metal nanostructured network can provide low resistance while providing good optical properties.Therefore, film is applicable makees Transparent conductive electrode or its analog.Transparent conductive electrode is suitably adapted for a series of applications, for example, connect along the light of solar cell Receive the electrode on surface.For display and especially touch-screen, film can be patterned to provide the conductive pattern formed by the film. Substrate with patterned film generally has good optical properties in the appropriate section of pattern.

The resistance of film can be expressed as sheet resistance, its with ohms per square (Ω/ or ohm/sq) be unit report with Separated to the block resistor tracks according to the parameter related with measurement process.The sheet resistance of film is surveyed usually using four-point probe Amount or another suitable process measurement.In certain embodiments, molten metal nanometer line network can have no more than about 300ohm/sq Sheet resistance；In a further embodiment, to be no more than about 200ohm/sq；In Additional examples of composition, for no more than about 100ohm/sq；And in other embodiments, to be no more than about 60ohm/sq.One of ordinary skill in the art it will be recognized that Cover the additional range and the scope of sheet resistance in above-mentioned clear and definite scope within the scope of the present invention.Depending on application-specific Fixed, the Commercial Code of the sheet resistance used for device can be not necessarily for relatively low sheet resistance value (such as when can relate to volume During outer cost), and correlation can be (such as) of the desired value as different quality and/or the touch-screen of size on Current commercial 270ohm/sq, to 150ohm/sq, to 100ohm/sq, to 50ohm/sq, to 40ohm/sq, to 30ohm/sq or less than 30ohm/sq, and each of these values are defined in the scope between the particular value as the end points of scope, such as 270ohm/ Sq to 150ohm/sq, 270ohm/sq to 100ohm/sq, 150ohm/sq to 100ohm/sq and its fellow, wherein defining 15 Individual particular range.Therefore, the film of lower cost is suitably adapted for some applications, and cost is appropriate higher sheet resistance value.Typically For, sheet resistance can be reduced by increasing the loading of nano wire, but for other angles, increased loading may be not It is desirable, and metal loads a factor in many factors for only reaching low sheet resistance value.

For the application as nesa coating, it is necessary to which molten metal nanometer line network maintains good optical transparency.It is former On then, optical clarity is reversely related to loading, wherein higher loading causes transparency to reduce, but the processing of network can also be shown Write influence transparency.In addition, polymer adhesive and other additives may be selected to maintain good optical transparency.Can be on saturating The light for being shot through substrate assesses optical clarity.For example, can by using UV visible spectrophotometers and measure via The total transmission of conducting film and support substrate measures the transparency of conducting film described herein.Transmissivity is transmitted intensity (I) with incident intensity (I_o) ratio.Can be by by the total transmittance measured (T) divided by the transmissivity through support substrate (T_sub) estimate the transmissivity (T via film_film).(T=I/I_oAnd T/T_sub=(I/I_o)/(I_sub/I_o)=I/I_sub=T_film)。 Therefore, the total transmission that recoverable is reported is to remove the transmission through substrate, so as to only obtain the transmission of film.Although it is generally desirable to With the good optical transparency across visible spectrum, but for convenience, the optical transmission of the light of 550nm wavelength can be reported. Alternatively or in addition, transmission can be reported as the total transmittance of the light of wavelength from 400nm to 700nm, and such result is reported in In following instance.Generally, for molten metal nano wire film, 550nm transmissivities and the total transmission from 400nm to 700nm The measurement result of rate (or only using " total transmittance " for convenience) is without qualitative difference.In certain embodiments, by melting network The film of formation has at least 80% total transmittance (TT%)；In a further embodiment, it is at least about 85%；Additionally implementing It is at least about 90% in example；In other embodiments, it is at least about 94%；And be from about 95% to about in certain embodiments 99%.Standard ASTM the D1003 (" turbidity of transparent plastic and luminous saturating can be used in the transparency of film on transparent polymer substrate Penetrate the standard method of test of rate ") to assess, the standard is incorporated herein by reference.The general technology people of art Member is it will be recognized that cover the additional range and the scope of the transmissivity in above-mentioned clear and definite scope within the scope of the present invention.When When the measured optical property of film is adjusted in the example of following substrate, film has fabulous transmission and turbidity value, and these properties connect Reach together with the low sheet resistance observed.

Molten metal network can also have the highly transmissive of low turbidity and visible ray, while having desirable low thin layer Resistance.The nephelometer based on above-cited ASTM D1003 can be used to measure turbidity, and can remove the turbidity contribution of substrate To provide the turbidity value of nesa coating.In certain embodiments, sintered network film can have no more than about 1.2% it is turbid Angle value；In a further embodiment, to be no more than about 1.1%；In Additional examples of composition, to be no more than about 1.0%；And other It is from about 0.9% to about 0.2% in embodiment.It is simultaneously real by the nano silver wire suitably selected as described in example The value of existing extremely low turbidity and sheet resistance.It is adjustable to load to balance sheet resistance value and turbidity value, wherein extremely low turbidity value May be still with good sheet resistance value.Specifically, it can be reached in the case where sheet resistance value is at least about 45ohm/sq Into no more than 0.8% and in a further embodiment from about 0.4% to about 0.7% turbidity value.In addition, can be in sheet resistance value It is to reach 0.7% to about 1.2% and in certain embodiments from about 0.75% in the case of about 30ohm/sq to about 45ohm/sq To about 1.05% turbidity value.All these films maintain good optical transparency.One of ordinary skill in the art will recognize Know, cover the additional range and the scope of turbidity in above-mentioned clear and definite scope within the scope of the present invention.

On the corresponding property of multilayer film, additional component is generally selected to have small influence on optical property, and it is commercially available Various coatings and substrate are in transparent element.Suitable optical coating, substrate and associated material is summarized in above. Some in structural material can be electric insulation, and if using compared with thick dielectric layer, then patternable film is to provide multiple positions Put, can provide the access of the conducting element embedded to script through the gap or space of insulating barrier at the position and electricity connects Touch.

Touch sensor

Nesa coating described herein, which can be effectively incorporated to, is suitably adapted for touch-screen for many electronic installations In touch sensor.Some representative embodiments are generally described herein, but nesa coating is applicable to other to be designed. The common attribute of touch sensor is usually to exist in its natural state (that is, when without touching or otherwise being connect through outside When touching) in two transparent conductive electrode structures for being spaced apart configuration.For the sensor based on capacitance operation, dielectric layer is usual Between two electrode structures.With reference to Fig. 3, the representational touch sensor 202 based on electric capacity include display module 204, can Select base substrate 206, it is the first transparent conductive electrode structure 208, dielectric layer 210 (for example, polymer or glass flake), second saturating Bright conductive electrode structure 212, optional top cover 214, and the measurement that the measurement electric capacity associated with the touch to sensor changes Circuit 216.With reference to Fig. 4, the representational touch sensor 240 based on resistance includes display module 242, optional lower substrate 244th, the electrode knot that the first transparent conductive electrode structure 246, the second transparent conductive electrode structure 248, support are configured in nature The supporting construction 250,252 of the configuration spaced apart of structure, upper cover layer 254 and resistance measuring circuit 256.

Display module 204,242 by (such as) LED-based display, LCD display or other can be wanted display module. Substrate 206,244 and coating 214,254 can be independent transparent polymeric sheet or other transparent sheets.Supporting construction can be by being situated between Electric material is formed, and sensor construction may include additional support to provide wanted stabilising arrangement.Measuring circuit 216,256 is in institute It is known in category field.

Molten metal network can be used to be effectively formed for transparent conductive electrode 208,212,246 and 248, molten metal network Different sensors can be formed through appropriate pattern, but molten metal network forms some transparency electrodes in certain embodiments Structure, and other transparent electrode structures in device may include for example as film or particle conducting metal oxide (for example Tin indium oxide, the zinc oxide of adulterated al, the cadmium oxide of doped indium, the tin oxide of fluorine of adulterating, the tin oxide of antimony dopant or its is similar Thing), CNT, graphene, the material of conductive organic composition or its analog.As described in this article, molten metal net Network can be effectively patterned, thereby increases and it is possible to needs to make the patterned film formation sensor in one or more electrode structures so that thoroughly Multiple electrodes in bright conductive structure can be used for providing the positional information related to touching process.Use the conductive electricity of patterned transparent Pole formed patterning touch sensor be described in such as palace sheet (Miyamoto) et al. it is entitled " touch sensor, with touch Touch the display of sensor and method (Touch Sensor, the Display With Touch for producing location data Sensor, and Method for Generating Position Data) " United States Patent (USP) 8,031,180 and sakata Et al. (Sakata) entitled " leading used in narrow frame touch input thin slice, its manufacture method and narrow frame touch input thin slice Electric thin slice (Narrow Frame Touch Input Sheet, Manufacturing Method of Same, and Conductive Sheet Used in Narrow Frame Touch Input Sheet) " open U.S. patent application case It is incorporated herein by reference in 2012/0073947, both this.

Example

Following instance is related in loaded polybenzazole precursor thing solution coating to appropriate substrate.Pass through Nano diamond Example is presented in filler, alumina nanoparticles filler or zirconium oxide nano-particle filler.Some examples are related to form passive state through painting Cloth polymer film.Other examples are related to the painting associated with causing the molten metal conductive network of the construction in nesa coating Layer.For the embodiment of nesa coating, by being led in the layer with molten metal conductive network or be placed in molten metal Example is presented in property enhancing nano-particle in coating above the layer of electric network.Molten metal conductive network is to use silver nanoparticle Line is formed.

Use average diameter between 25nm and 50nm in following instance and average length is 10 microns to 30 microns of business Industry nano silver wire.Nano silver wire ink is substantially as the entitled of Lee (Li) et al. " is used to be formed and led with melting the transparent of network Metal nanometer line ink (the Metal Nanowire Inks for the Formation of Transparent of electrolemma Conductive Films With Fused Networks) " the same U.S. patent application case 14/448,504 in application Example 5 described in, the patent application case is incorporated herein by reference.Metal nanometer line ink includes The nano silver wire of amount between 0.01wt% to 0.5wt%；Silver ion between 0.01mg/ml and 2.0mg/ml；And concentration is About 0.02wt% to the 1.0wt% adhesive based on cellulose.Nano silver wire ink is the aqueous solution with a small amount of alcohol.Ink Water is by slot coated to PET polyester films.After coating nano wire ink, film then heats 10 at 100 DEG C in an oven Minute is with the dry film.The formation program of the external coating described in specific examples below.

The total transmission (TT) and turbidity of membrane sample are measured using nephelometer.In order to adjust the turbidimetry knot of following sample Really, substrate turbidity value can be subtracted from measurement result, so as to only obtain the substantially turbidity measurements of nesa coating.Instrument is passed through Design is with based on the standards of ASTM D 1003 (" turbidity of transparent plastic and the standard method of test of luminous transmittance ") assessment optics Property, the standard is incorporated herein by reference.The total transmission and turbidity of these films include PET substrate, PET substrate Basic total transmission and turbidity are respectively about 92.9% and 0.1% to 0.4%.In the following example, molten metal nano wire is presented Some different composites and optics of ink and sheet resistance measurement result.

By 4 point probe methods, contactless ohmer or by measuring the resistance of film (by using by by silver paste shape Into the square that defines of two solid (opaque) silver wires) measurement sheet resistance.In certain embodiments, it is progress thin-layer electric Resistance measurement, sometimes using a pair of parallel silver paste band, it is formed in the following manner：Slurry is coated onto on the surface of sample With define square or rectangular shape, then at substantially 120 DEG C by sample anneal 20 minutes so as to solidify and dry silver paste. Crocodile clip is connected to silver paste band, and connects the line to business electric resistance measuring apparatus.So that being electrically connected to the exposure of film End sections.The sheet resistance of some samples is measured by third-party vendor.

The pencil hardness of AgNWs membrane samples is measured using pencil protos test suite PROTOS.Pencil sharpening method is followed, sand paper is used In modification tip of a pencil, and pencil is applied constant downward force while keeping 45° angle, and making pencil across the surface of membrane sample It is mobile.This test uses 500g or 750g business pencil hardness external members.By analyzing the pencil of different graphite deciding grade and level scales to base The influence of bottom conductive layer determines hardness.If do not caused damage to basalis, then think film for the particular graphite Grade is qualified.Film is checked with 20 × magnifying power under Leica microscope.Film is placed on the flat surfaces of pole, this is for being avoided by lead Pen scraping is particularly significant, because the film is very thin.This test is different from correspondence standardized test, and standardized test is depended on need not The visual inspection of amplification.

The steel wool final hardness of membrane sample is measured using ultra-fine 0000 steel wool for bearing specified weight.For some samples Product, make the steel wool by the constant downward force provided by 20g, 50g or 100g weight above coated film by once, And check film under light to detect scratches.The number of scratch determines the Scratch Resistance of the film.What steel wool of having no way of was caused scrapes Trace will imply that the specified weight " qualified " being subject to for steel wool.Under not qualified situation, institute is indicated in result part The number of the scratch caused.For some samples, turbidity and/or sheet resistance are also assessed after steel wool test.

When analyzing turbidity and/or sheet resistance, by extra-fine steel velvet for rubbing after coating and being crosslinked external coating Surface.While constant downward force is kept, pole mildly performs steel wool friction.Rubbed tested person film back and forth with steel wool One section 10 times.Compared to deeper scratch, the influence that scratches often increase turbidity is much smaller.By BYKHaze-Gard Plus is used for overall clarity and turbidimetry.The sheet resistance that internal OC composites are also measured by third party's service changes Become, as described in example 4.Turbidity is measured before test and afterwards.

Influence of the example 1- Nano diamonds to the business external coating in transparent substrates

The test of this example is to the Nano diamond that is mounted with the PET substrate with initial polymer adhesive external coating The influence of the hardness of business external coating.

The preparation of substrate be by be coated with the polymer adhesive based on cellulose base ink but will be any Nano silver wire is applied on transparent PET substrate and dried.Coated substrate has 0.72% turbidity.From the farsighted conjunction strain formula of enlightening The business coated polymeric of commercial firm is dissolved in N,N-dimethylformamide (DMF).Prepare six samples, wherein each two sample Polymer concentration one of for 2wt%, 3wt% and 4wt%.In a sample in each polymer concentration, respectively The Nano diamond of the hydrogen end-blocking of 0.2wt%, 0.3wt% or 0.4wt% concentration is added, to cause each containing diamond In sample, diamond concentration is about 1/10th of polymer concentration.By slot coated by coating solution with 1 mil (25.4 Micron) wet thickness deposited on substrate.Film is then dried by infrared lamp and existed using the deep system (H types bulb) of He Lishi spokes 1J/cm²Under UV photocurings are used in nitrogen.The solids content of coating solution is related to the thickness through dry film, and with having The film of the coating solution formation of 0.3wt% polymer is by the average thickness with about 75nm.With nanoparticulate fillers Compared hardness and optical property between the film of formation and the film formed without nanoparticulate fillers.As a result it is showed in table 1.Typically For, for thicker through dry coating, significantly improve hardness turbidity increase simultaneously comprising Nano diamond few.

Table 1

Sample	Polymer wt% in solution	Nano diamond wt% in solution	TT%	Turbidity %	Pencil hardness
						1	2	0	91.6	0.64	<9B
2	2	0.2	92.5	0.62	<9B
						3	3	0	92.5	0.61	<9B
4	3	0.3	92.5	0.69	9B-8B
						5	4	0	92.4	0.59	8B
6	4	0.4	91.5	1.00	5H

The influence of Nano diamond in example 2- conductive inks

The hardness of film of this example test with molten metal nanostructured layers, the film, which has, to be incorporated into conductive layer Nano diamond, hard coat is above the conductive layer.

Nano silver wire ink is prepared as described above, but addition 0.036wt% has the table that hydrogen is blocked in the ink The Nano diamond in face.Before being mixed into nano silver wire ink, originally Nano diamond is scattered in gamma-butyrolacton solvent In.Nano wire ink to be formed the melting of conductive layer in slot coated to PET film substrate and through drying so that nano wire to be molten to In metal Nano structure network.Prepare outer coating composition as described in example 1, but polymer concentration in 0.5wt% and Without Nano diamond.With described in example 1 similarly by slot coated on through dry molten metal conductive layer, do Dry coating and UV solidification coating and process external coating.

The film formed in the case of having nanoparticulate fillers in the conductive layer and the film formed without nanoparticulate fillers Between compare hardness and optical property, as shown in table 2.Also determine there is external coating and optical property during without external coating.Receiving The hardness of the film with external coating is significantly improved in rice noodles ink comprising Nano diamond.In the situation of addition Nano diamond Under, sheet resistance is slightly improved, overall clarity is somewhat reduced, and slightly improves turbidity.It should be noted that but external coating generally phase Turbidity is reduced for the corresponding sample without external coating.

Table 2

Sample	Turbidity %	TT%	Sheet resistance (ohm/sq)	Pencil hardness
					AgNW inks	1.11	92.2	58
AgNW inks+external coating	0.91	91.9		2H
					AgNW inks with Nano diamond	1.33	91.2	87
AgNW inks+external coating with Nano diamond	1.19	91.4		~8H

The influence of the Nano diamond in business external coating above example 3- transparency conducting layers

The test of this example incorporates the hardness of the nesa coating of business external coating (it incorporates Nano diamond).

Deposit and process as described above nano silver wire.After drying, layer is included in molten in sparse metal conducting layer Melt metal Nano structure network.The sheet resistance of conductive layer between 50 and 60ohm/sq, and coating and curable overcoat it Afterwards, thin external coating does not significantly change the sheet resistance of film.Test business external coating different from 3, three different correspondence solvents System and two different metal nano wire inking systems of the initial nanodiamond liquid dispersion combination of three kinds of differences.With melting gold Belong to the substrate of nanostructured network has 1.12% (the first inking system and 1.28% (the second ink before coating external coating System) initial haze.It is harder between the film formed with nanoparticulate fillers and the film formed without nanoparticulate fillers Degree and optical property.

The outer painting formed by the first nano silver wire inking system and with the coating material from mixed plastic Co., Ltd Layer prepares first group of sample.The coating solution for external coating is formed in formic acid solution.It is dense with the polymer with 0.5wt% Two kinds of solution of degree and two kinds of solution, four kinds of solution of formation of the polymer concentration with 0.75wt%.Dense in each polymer Among two kinds of solution of degree, a kind of solution adds business Nano diamond in aqueous solvent.With nano-diamond filler Solution have 0.05wt% Nano diamonds (for 0.5wt% polymer solution) and 0.075wt% Nano diamonds (right In 0.75wt% polymer solution).External coating is coated, dries and solidifies.Optical measurement and hardness are obtained in cured film Measure, and result is presented in table 3.Turbidity value in table 3 is the average value across the film, and the primary cloudy that steel wool is assessed Angle value is the particular value measured at the place of application steel wool.As shown in table 3, it is aobvious comprising Nano diamond in these films Write and improve hardness, and corresponding experiment also shows to significantly improve the repellence for the scratch for causing steel wool.Shown in Fig. 5 and 6 The representative scanning electron microscopy of two kinds of magnifying powers of 10wt% nano-diamond membrane.In order to compare, Fig. 7 and 8 is opened up respectively Show the SEM image of 5wt% and 3wt% nano-diamond membrane.

Table 3

Two additional samples are prepared by formic acid.These solution are public by California hard conating in coating solution (CHC) polymer is taken charge of to prepare.Coating solution has 0.5wt% polymer.A kind of solution includes in aqueous solution 0.05wt% business Nano diamond and the second solution does not include any Nano diamond.With the second nano silver wire ink system The coating solution above the molten metal nanostructured network that system is formed.Optics and hardness knot are obtained after drying and solidification Really, and result is presented in table 4.Significantly improve the hardness of coating comprising Nano diamond and reduce and test what is produced by steel wool Turbidity is improved.Initial haze is merely due to Nano diamond is somewhat improved and total transmittance is only slightly reduced.

Table 4

Another group of 9 samples are prepared by the N,N-dimethylformamide in coating solution.Solution covering is farsighted from enlightening Three kinds of different polymer concentrations of the coated polymeric of Co., Ltd. are closed, and some samples include corresponding concentration in coating solution The Nano diamond being originally scattered in ethylene glycol, and other solution do not include Nano diamond.Black with the first nano wire Applying coating above the molten metal nanostructured network of aqueous solution formation.After drying and curable overcoat obtain optics and Hardness measurement, and result is summarized in table 5.

Table 5

Other 10 samples are prepared in non-aqueous solvent to form external coating.Again, with 4.5 volumes hundred Used in propylene glycol monomethyl ether (PGME) solvent of the DMAC N,N' dimethyl acetamide (DMA) of point ratio from Diruihe Co., Ltd. Polymer.All solution include 0.5wt% polymer.Using three kinds of different business Nano diamonds, and received for every kind of Rice diamond, uses three kinds of different Nano diamond concentration.Nano diamond is with the dispersion liquid (ND-A) in ethylene glycol, tool There is the ethylene glycol dispersion liquid (ND-H-EG) of particle (it has the surface that hydrogen glycol is blocked) or (it has hydrogen end-blocking with particle Surface) gamma-butyrolacton dispersion liquid (ND-H-G) form obtain business Nano diamond.Film sample is prepared as described above Product.Obtain optics and hardness measurement.For these samples, scratches analysis is performed also after being rubbed by steel wool.As a result It is showed in table 6.Nano-particle significantly improves the Scratch Resistance of film, and turbidity increase and total transmittance reduction are few.

Table 6

The influence of Nano diamond in coating solution formulated example 4-

In this example, check that Nano diamond changes in the sample of the nesa coating of the external coating with inside allotment Enter the validity of hardness.

For these experiments, led by using the molten metal for the second metal nanometer line ink formation being described in example 3 Electric layer prepares substrate.Test two kinds of different inside coating solutions (HOC1 and HOC2).The coating material of inside allotment includes business The admixture of the cross-linking acrylate hard coats compositions of industry UV and annular siloxane epoxy resin.HOC1 further comprises propylene Acid amide carbamate oligomer, and HOC2 further comprises epoxy acrylic oligomer ester.Epoxy acrylate mixing hard conating It is further described in the following：For example, entitled " the curable hard coating composition of wear-resistant ultraviolet ray of clock (Chung) (Abrasion Resistant Ultraviolet Light Curable Hard Coating Compositions) " U.S. State's patent 4,348,462；The entitled of this Tener (Kistner) of base " is used for the protective coating (Protective that light has Coating for Phototools) " United States Patent (USP) 4,623,676；And Sheng Jieermanuo (Sangermano) et al. topic For " UV solidifies IPN epoxy acrylic polymer network：Prepare and characterize (UV-Cured Interpenetrating Acrylic-Epoxy Polymer Networks:Preparation and Characterization)” (Macromolecular Materials and Engineering, volume 293, page 515 to 520 (2008)), Suo Yousan Person is incorporated herein by reference.

12 samples are prepared by two different solvents systems.Specifically, eight samples are with by 1:1 stereometer Prepared by the mixture of DMF (DMF) and methyl ethyl ketone (MEK), and three samples are prepared with acetonitrile.Sample Product 1 to 4 are prepared by HOC1, and sample 5 to 12 is prepared by HOC2.Pass through two kinds of different polymer in coating solution Concentration and three kinds of different Nano diamond concentration prepare sample.Sample 1 to 8 has 0.5wt% polymer, and sample 9 to 12 Polymer with 0.8wt%.For four samples, in addition to optical measurement and hardness measurement, also measure and applying steel wool The change of sheet resistance afterwards.As a result it is presented in table 7 (sample 1 to 8) and table 8 (sample 9 to 12).As a result solvent pair is shown Coating performance, which has, to be significantly affected.Nano diamond significantly improves hardness.Turbidity is slightly improved comprising Nano diamond.

Table 7

Table 8

Six samples are prepared by the external coating based on HOC2.On the whole, two different solvents systems and two are tested Individual different types of Nano diamond.Sample is prepared as described above.As a result it is presented in table 9.As presented in table 7 and 8 As a result, hardness result significantly depends on solvent system.

Table 9

Sample	Nano diamond wt%, type	Solvent (v:v)	Pencil hardness
				1	0.03,ND-H-EG	Acetonitrile+DMA (95:5)	HB
2	0.05,ND-H-EG	Acetonitrile+DMA (95:5)	3H
				3	0.03,ND-H-G	Acetonitrile+DMA (95:5)	3H
4	0.05,ND-H-G	Acetonitrile+DMA (95:5)	2H
				5	0.03,ND-H-G	Acetonitrile+PGME+DMA (48:48:4)	4H
6	0.05,ND-H-G	Acetonitrile+PGME+DMA (48:48:4)	6H

Example 5- metal oxide fillers

Metal oxide nanoparticles of this example test in the external coating above sparse metal conducting layer are led to transparent The influence of electrolemma.

Conductive layer is formed with the second nano silver wire ink as described in example above 3.Applied outside by two kinds of differences One of one polymer and one of three kinds of different metal oxides nano-particles prepare six paintings through mixing well Cloth solution example.First external coating polymer is obtained from California hard conating company (CHC), and the second external coating polymerize Thing is analogous to (HOC3) that polymer is internally allocated being described in example 4.Metal oxide nanoparticles are from BYK And both US-Nano alumina nanoparticles (Al₂O₃) or zirconium oxide nano-particle (ZrO from BYK₂).As retouched above Coating is stated, is dried and solidifies all external coating solution.The mean size of nano-particle is about 20nm to about 40nm.Coating solution has There are about 0.75wt% polymer and about 0.09wt% nano-particle.

Film that acquisition is formed with metal oxide nanoparticles and the film that is formed without metal oxide nanoparticles it is thin Layer resistance (SR) and optical property, and result is presented in table 9.In general, received comprising alumina nanoparticles or zirconium oxide Rice corpuscles does not significantly improve sheet resistance or reduction total transmittance.In the case of zirconium oxide nano-particle, turbidity is not carried It is high and can somewhat reduce.However, in the case of alumina nanoparticles, turbidity is significantly improved.

Table 10

Above example is intended to illustrative and not restrictive.Additional examples of composition is in claims.In addition, Although describing the present invention with reference to specific embodiment, those skilled in the art will be appreciated that can be without departing substantially from the present invention Spirit and scope in the case of change is made in terms of form and details.It is any of the above described by reference to document carry out and Enter to be restricted so that the subject matter of the content contradiction with clearly disclosing herein will not be incorporated to.

Claims (26)

1. a kind of optical texture, it includes transparent substrates and the coating including polymer adhesive and Nano diamond.

2. optical texture according to claim 1, it has from about 0.01 weight % to about 30 weight % nanometer Buddha's warrior attendant Stone.

3. the optical texture according to claim 1 or claim 2, wherein the transparent substrates are included with micro- from about 5 Polymer film of the rice to 2 millimeters of average thickness.

4. the optical texture according to any claim in Claim 1-3, wherein the coating have from about 50nm to About 25 microns of average thickness.

5. the optical texture according to any claim in claim 1 to 4, wherein the polymer adhesive includes gathering Siloxanes, polysilsesquioxane, polyurethane, acrylic resin, acrylic acid series copolymer, cellulose ether and cellulose esters, nitre Cellulose, other structural polysaccharides for being insoluble in water, polyethers, polyester, polystyrene, polyimides, fluoropolymer, benzene second Alkene-acrylate copolymer, SB, acrylonitrile butadient styrene, polysulfide, contain The polymer of epoxy radicals, its copolymer and its mixture.

6. the optical texture according to any claim in claim 1 to 5, wherein the coating is led including sparse metal Electric device.

7. the optical texture according to any claim in claim 1 to 5, it further comprises adjacent with the coating Sparse metal conducting layer.

8. the optical texture according to any claim in claim 1 to 7, wherein the coating has than without filler Clear coat hard at least about 1 grade of pencil hardness pencil hardness.

9. a kind of nesa coating, it includes transparent substrates, transparency conducting layer and including polymer adhesive and nano-particle Protective coating, the nano-particle has no more than about 100nm average primary particle diameter, is formed by following material：Have The material of at least about 1650HV block Vickers hardness；High thermal conductivity material, it is selected from the group being made up of the following：Buddha's warrior attendant Stone, graphene, silicon nitride, boron nitride, aluminium nitride, GaAs, indium phosphide or its mixture；And/or high dielectric constant material, its Selected from the group being made up of the following：Barium titanate, strontium titanates, lead titanates, lead zirconium titanate, CaCu 3 Ti 4 O and its mixture.

10. nesa coating according to claim 9, wherein the transparency conducting layer includes sparse metallic conductive element.

11. nesa coating according to claim 9, wherein the transparency conducting layer includes molten metal nano junction network forming Network.

12. nesa coating according to claim 9, wherein the transparency conducting layer includes electrically conducting transparent inorganic oxide Thing, CNT, graphene or its combination.

13. the nesa coating according to any claim in claim 9 to 12, its have from about 0.01 weight % to About 30 weight % nano-particle.

14. the nesa coating according to any claim in claim 9 to 12, wherein the protective coating have from About 0.1wt% to about 70wt% nano-particle, it has no more than about 50nm mean particle diameter, and wherein described polymerization Thing adhesive includes polysiloxanes, polysilsesquioxane, polyurethane, acrylic resin, acrylic acid series copolymer, cellulose ether And cellulose esters, nitrocellulose, other structural polysaccharides for being insoluble in water, polyethers, polyester, polystyrene, polyimides, fluorine It is polymer, copolymer in cinnamic acrylic ester, SB, acrylonitrile butadient styrene, poly- Sulfide, the polymer containing epoxy radicals, its copolymer and its mixture.

15. the nesa coating according to any claim in claim 9 to 14, wherein the substrate is with from about The polymer film of 5 microns to 1 millimeter of average thickness, and wherein described coating has the average thickness from about 50nm to about 25 micron Degree.

16. the nesa coating according to any claim in claim 9 to 15, wherein the nano-particle includes receiving Rice diamond.

17. the nesa coating according to any claim in claim 9 to 16, wherein the coating have than without The big at least about 1 grade pencil hardness of the pencil hardness of the clear coat of filler and no more than about percent 5 be attributed to it is described The reduction of the total transmission value of the visible ray of bright coating.

18. a kind of nesa coating, it includes transparent substrates and including polymer adhesive, sparse metallic conductive element and nanometer The transparency conducting layer of particle, the nano-particle has no more than about 100nm average primary particle diameter, is formed by following material： The material of block Vickers hardness with least about 1650HV；High thermal conductivity material, it is selected from the group being made up of the following： Diamond, graphene, silicon nitride, boron nitride, aluminium nitride, GaAs, indium phosphide or its mixture；And/or high-k material Material, it is selected from the group being made up of the following：Barium titanate, strontium titanates, lead titanates, lead zirconium titanate, CaCu 3 Ti 4 O and its mixing Thing.

19. a kind of optical texture, it includes transparent substrates including polymer adhesive and from about 0.01 weight % to about 30 weights The clear coat of % nano-particle is measured, the nano-particle has no more than about 100nm average primary particle diameter；And institute Stating clear coat has the pencil hardness and no more than about 5 bigger at least about 1 grade than the pencil hardness of the clear coat without filler The total transmission reduction of the visible ray for being attributed to the transparent hard-coating layer of percent transmission.

20. optical texture according to claim 19, wherein what the clear coat had from about 50nm to about 25 micron Thickness.

21. a kind of solution, it includes solvent, curable polymer adhesive and nano-particle, and the nano-particle, which has, not to be surpassed Cross about 100nm average primary particle diameter and including：The material of block Vickers hardness with least about 1650HV；With extremely The high thermal conductivity material of few about 30W/ (mK) block thermal conductivity；High dielectric material, it is selected from the group being made up of the following Group：Barium titanate, strontium titanates, lead titanates, lead zirconium titanate, CaCu 3 Ti 4 O and its mixture；Or its mixture.

22. solution according to claim 21, it has from about 0.005wt% to about 5wt% nano-particle.

23. the solution according to claim 21 or claim 22, wherein the nano-particle includes Nano diamond.

24. the solution according to any claim in claim 21 to 23, wherein the solvent include water, it is ethanol, different Propyl alcohol, isobutanol, the tert-butyl alcohol, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclic ketone, glycol ethers, toluene, hexane, ethyl acetate, Butyl acetate, ethyl lactate, propylene carbonate, dimethyl carbonate, PGMEA (acetic acid 2- methoxyl group -1- Methylethyls ester), N, N- Dimethylformamide, DMAC N,N' dimethyl acetamide, acetonitrile, formic acid or its mixture.

25. the solution according to any claim in claim 21 to 24, wherein the curable polymer adhesive Including polysiloxanes, polysilsesquioxane, polyurethane, acrylic resin, acrylic acid series copolymer, cellulose ether and cellulose Ester, nitrocellulose, other structural polysaccharides for being insoluble in water, polyethers, polyester, copolymer in cinnamic acrylic ester, benzene second Alkene-butadiene copolymer, acrylonitrile butadient styrene, polysulfide, the polymer containing epoxy radicals, its copolymer And its mixture.

26. the solution according to any claim in claim 21 to 25, it has from about 0.025wt% to about 50wt% polymer-bonded agent concentration and from 0.005wt% to about 5wt% nanoparticle concentration.